Hydrochloric Acid → 2,3-Piperidinedione 3-(3-bromophenyl)hydrazone

HRID 1515468Notes

Reaction equation

HRID 1515468 reaction equation
C([CH:6]1[CH2:11][CH2:10][CH2:9][NH:8][C:7]1=[O:12])(OCC)=O.[OH-].[K+].[Br:15][C:16]1[CH:17]=[C:18]([CH:20]=[CH:21][CH:22]=1)[NH2:19].Cl.[N:24]([O-])=O.[Na+].NC(N)=O.N(O)=O.C(=O)([O-])[O-].[Na+].[Na+]>O>[Br:15][C:16]1[CH:17]=[C:18]([NH:19][N:24]=[C:6]2[CH2:11][CH2:10][CH2:9][NH:8][C:7]2=[O:12])[CH:20]=[CH:21][CH:22]=1

Participants

10

Reactant 8

HCID 313Hydrochloric AcidHCID 1176UreaHCID 10340Sodium CarbonateHCID 115623-BromoanilineHCID 14797Potassium HydroxideHCID 24529Nitrous AcidHCID 977733-Carbethoxy-2-piperidoneHCID 23668193Sodium Nitrite

Product 1

HCID 866498322,3-Piperidinedione 3-(3-bromophenyl)hydrazoneYield 32.3%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Conditions

Temperature
0 °C

Procedure

3-Carbethoxy-2-piperidone (4.7 g, 27.4 mmol) is stirred with potassium hydroxide (1.64 g) in water (56 mL) and kept at 30° C. on an oil bath overnight. 3-Bromoaniline (4.99 g, 29 mmol) is treated with water (50 mL) and concentrated HCl (10 mL) and cooled to 0° C. Sodium nitrite (2.46 g, 35 mmol) in water (9 mL) is added dropwise to the above solution at 0° C. and stirred for an additional 20 minutes. Urea is added to decompose the excess nitrous acid, and the diazotized solution is neutralized with 10% aqueous sodium carbonate solution (45-50 mL). The resulting solution is filtered into the solution of previously hydrolyzed 3-carbethoxy-2-piperidone (2-piperidone-3-carboxylic acid) at 0° C. After a few minutes, glacial acetic acid is added to bring the pH of the solution to 3-4. The reaction mixture is stirred at 0° C. for 5-6 h, and the yellow precipitate which resulted is filtered, washed with water, and dried to get the title compound (2.5 g, 32% yield).

Workup

  1. filtrationThe resulting solution is filtered into the solution of previously hydrolyzed 3-carbethoxy-2-piperidone (2-piperidone-3-carboxylic acid) at 0° C
  2. waitAfter a few minutes
  3. additionglacial acetic acid is added
  4. stirringThe reaction mixture is stirred at 0° C. for 5-6 h
  5. customthe yellow precipitate which resulted
  6. filtrationis filtered
  7. washwashed with water
  8. customdried

Sources & evidence

ORD record
ord-1dee2a73a72c4eb0a183aacc44dddf73
Source dataset
uspto-grants-2012_07
Patent number
US08222424B2

Reaction notes

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